Novel Block Polymers and Cosmetic Compositions and Processes Comprising Them

ABSTRACT

The present invention relates to novel block polymers comprising at least one first block and at least one second block that are incompatible with each other, have different glass transition temperatures (Tg), and are linked together via an intermediate segment comprising at least one constituent monomer of the at least one first block and at least one constituent monomer of the at least one second block. The block polymer has a polydispersity index I of greater than 2. The invention also relates to cosmetic compositions comprising the block polymers and processes for their use.

This application claims priority under 35 U.S.C. § 119 to French PatentApplication Nos. 0211949, filed Sep. 9, 2002, and 02306121, filed May21, 2003, both of which are hereby incorporated by reference.

The present invention relates to novel polymers of specific structure.

The present invention also relates to cosmetic compositions comprisingsuch polymers.

Various types of polymers are conventionally used in cosmeticcompositions because of the various properties that they can give tothese compositions.

Polymers are used, for example, in makeup or care compositions for theskin, the lips, or the integuments, such as nail varnishes or haircarecompositions.

However, when a formulator is using two polymers that are incompatible,i.e., immiscible in the same solvent, within the same composition, theformulator is confronted with problems of phase separation ordecantation, and in general with the production of a non-uniformcomposition. These problems could only be solved hitherto by thepresence in the composition of a compound for rendering the polymersmutually compatible.

The present inventors thus proposes a polymer which, when included in acomposition, for example a cosmetic composition, enables the compositionto avoid the drawbacks, limitations, defects and disadvantages of thecompositions of the prior art.

The inventors have found that these drawbacks, limitations, defects, ordisadvantages may be avoided by means of a polymer, referred to as ablock polymer, comprising at least one first block and at least onesecond block that are incompatible with each other and that havedifferent glass transition temperatures (Tg), the at least one first andat least one second blocks being linked together via at least oneintermediate segment comprising at least one constituent monomer of theat least one first block and at least one constituent monomer of the atleast one second block, and where the polymer has a polydispersity indexI of greater than 2.

The expression “at least one block” means one or more blocks.

The expression blocks “that are incompatible with each other” means thatthe mixture of the polymer formed by the at least one first block andthe polymer formed by the at least one second block (hereinafterreferred to as “the polymer mixture”) is immiscible in the mainpolymerization organic solvent of the block copolymer at roomtemperature (25° C.) and atmospheric pressure (10⁵ Pa), at a content ofthe polymer mixture greater or equal to 5% by weight of the total weightof polymers and solvent, and wherein

(i) the polymer formed by the at least one first block and the polymerformed by the at least one second block are present in the polymermixture in a ratio ranging from 10/90 to 90/10 by weight, and

(ii) each of the polymer formed by the at least one first block and thepolymer formed by the at least one second block has an average molarmass (weight-average or number-average molar mass) equal to the averagemass of the block polymer +/−15%.

The expression “main polymerization organic solvent” means, in the casewhere there is a mixture of polymerization solvents, the polymerizationsolvent which has the highest content by weight relative to the totalweight of the organic polymerization solvents. In the case where thereis a mixture of polymerization solvents and two or more of the solventsare present in identical weight ratios, the polymer mixture isimmiscible in at least one of the solvents. In the case where thepolymerization is made in a single solvent, the single solvent is themain solvent.

The at least one intermediate segment is a block comprising at least oneconstituent monomer of the at least one first block and at least oneconstituent monomer of the at least one second block of the polymer andallows these blocks to be “compatibilized.”

By incorporating these novel polymers into cosmetic compositions, thepresent inventors have discovered that some of these polymers, describedin greater detail below, may have advantageous cosmetic properties. Ingeneral, these polymers may be incorporated into compositions to a highsolids content, for example greater than 10% by weight relative to thetotal weight of the composition, and are easy to formulate. When used inhaircare products, they may improve at least one of styling power andsuppleness. They may increase the impact strength of nail varnishes andmay improve the staying power of a wide variety of makeup compositionswithout causing the user any discomfort.

Disclosed herein is also a cosmetic composition comprising such apolymer.

Further disclosed herein is a cosmetic makeup or care process forkeratin materials, comprising applying to the keratin materials acosmetic composition as disclosed herein.

Also disclosed is a method for improving the staying power of acomposition comprising providing a polymer as disclosed herein in acosmetic composition, as an agent for improving the staying power of thecomposition.

Finally, disclosed herein is the use of the polymer as disclosed in acomposition with improved staying power properties.

In one embodiment, the block polymer of the composition disclosed hereinmay be a film-forming linear block ethylene polymer.

The term “ethylene polymer” as defined herein is understood to mean apolymer obtained by the polymerization of monomers containing anethylenically unsaturated group.

The term “block polymer” is understood to mean a polymer comprising atleast two separate blocks, for example, at least three separate blocks.

The polymer may be a polymer with a linear structure. In contrast, apolymer having a non-linear structure may be, for example, a polymerwith a branched, star, grafted, or other structure.

The term “film-forming polymer” is understood to mean a polymer capableof forming, by itself or in the presence of at least one auxiliaryfilm-forming agent, a continuous film that adheres to a support, forexample, to keratinous materials.

In one embodiment, the polymer disclosed herein does not comprise anysilicon atoms in its skeleton. The term “skeleton” means the main chainof the polymer, as opposed to the pendent side chains.

In one embodiment, the polymer disclosed herein may not bewater-soluble, that is to say the polymer may not be soluble in water orin a mixture of water and linear or branched lower monoalcohols havingfrom 2 to 5 carbon atoms, chosen from ethanol, isopropanol, andn-propanol, without pH modification, with an active material content ofless than 1% by weight, at room temperature (25° C.).

In one embodiment, the polymer disclosed herein may not bewater-soluble, i.e., the polymer may not be soluble in water or in amixture of water and hydrophilic organic solvent(s) without pHmodification, with an active material content of at least 1% by weight,at room temperature (25° C.).

The expression “hydrophilic organic solvent” means alcohols and forexample linear and branched lower monoalcohols containing from 2 to 5carbon atoms, for example ethanol, isopropanol, and n-propanol, andpolyols, for example glycerol, diglycerol, propylene glycol, sorbitol,and pentylene glycol, and polyethylene glycols, hydrophilic C₂ ethers,and C₂-C₄ aldehydes.

In one embodiment, the polymer disclosed herein is not an elastomer.

The expression “non-elastomeric polymer” means a polymer which, whensubmitted to a stretching stress (for example when stretched by 30% ofthe original length) does not return to approximately its originallength when released. Specifically, “non-elastomeric polymer” means apolymer with an instantaneous recovery R_(i)<50% and a delayed recoveryR_(2h)<70% after having undergone a 30% elongation. In one embodiment,R_(i) is <30% and R_(2h) is <50%.

The elastomeric nature of the polymer may be determined according to thefollowing protocol:

A polymer film is prepared by pouring a solution of the polymer into aTeflon-coated mold followed by drying for 7 days under ambientconditions regulated to 23±5° C. and 50±10% relative humidity.

A film about 100 μm thick is thus obtained, from which are cut forexample, rectangular specimens (for example using a punch) 15 mm wideand 80 mm long.

This sample is subjected to a tensile stress using a machine sold underthe reference Zwick, under the same temperature and humidity conditionsas for the drying operation.

The specimens are drawn at a speed of 50 mm/minute and the distancebetween the jaws is 50 mm, which corresponds to the initial length (Lo)of the specimen.

The instantaneous recovery R_(i) is determined in the following manner:

-   -   the specimen is stretched by 30% (ε_(max)), i.e. about 0.3 times        its initial length (Lo)    -   the stress is released by applying a return speed equal to the        tensile speed, i.e., 50 mm/minute, and the residual elongation        percentage of the specimen, after returning to zero stress        (ε_(I)), is measured.

The percentage instantaneous recovery (R_(i)) is given by the formulabelow:R _(i)=((ε_(max)−ε_(i))/ε_(max))×100

To determine the delayed recovery, the residual percentage degree ofelongation of the specimen (ε_(2h)) is measured 2 hours after returningto zero stress.

The delayed recovery in % (R_(2h)) is given by the formula below:R _(2h)=((ε_(max)−ε_(2h))/ε_(max))×100

For example, in one embodiment, the polymer has an instantaneousrecovery R_(i) of 10% and a delayed recovery R_(2h) of 30%

The polymer disclosed herein comprises at least one first block and atleast one second block that are incompatible with each other and thathave different glass transition temperatures (Tg), the at least onefirst and second blocks are linked together via at least oneintermediate segment comprising at least one constituent monomer of theat least one first block and at least one constituent monomer of the atleast one second block, the polymer having a polydispersity index I ofgreater than 2.

It is pointed out that, in the text hereinabove and hereinbelow, theterms “first” and “second” blocks do not in any way condition the orderof the blocks in the structure of the polymer.

The polydispersity index I of the polymer may be equal to the ratio ofthe weight-average mass Mw to the number-average mass Mn.

The weight-average (Mw) and number-average (Mn) molar masses aredetermined by gel permeation liquid chromatography (THF solvent,calibration curve established with linear polystyrene standards,refractometric detector).

The weight-average mass (Mw) of the polymer disclosed herein may be, forexample, less than or equal to 300 000, for example ranging from 35 000to 200 000, and as a further example, from 45 000 to 150 000.

The number-average mass (Mn) of the polymer disclosed herein may be, forexample, less than or equal to 70 000, for example ranging from 10 000to 60 000, and as a further example, ranging from 12 000 to 50 000.

The polydispersity index of the polymer disclosed herein may be greaterthan 2, for example ranging from 2 to 9, in one embodiment greater thanor equal to 2.5, for example ranging from 2.5 to 8, and in anotherembodiment greater than or equal to 2.8, and for example ranging from2.8 to 6.

Each block of the polymer disclosed herein may be derived from one typeof monomer or from several different types of monomers. This means thateach block may comprise a homopolymer or a copolymer. The copolymerconstituting the block may in turn be random or alternating.

In one embodiment, the at least one intermediate segment comprising atleast one constituent monomer of the at least one first block and atleast one constituent monomer of the at least one second block of thepolymer is a random polymer.

For example, the at least one intermediate segment may be at least 85%derived from constituent monomers of the at least one first block and ofthe at least one second block, as a further example at least 90%, inanother example 95%, and as another example 100%.

In one embodiment, the at least one intermediate segment has a glasstransition temperature Tg that is between the glass transitiontemperatures of the at least one first and at least one second blocks.

As disclosed herein, the at least one first and second blocks may havedifferent glass transition temperatures.

The glass transition temperatures indicated for the at least one firstand second blocks may be theoretical Tg values determined from thetheoretical Tg values of the constituent monomers of each of the blocks,which may be found in a reference manual for example, the PolymerHandbook, 3rd Edition, 1989, John Wiley, which is hereby incorporated byreference, according to the following relationship, known as Fox's law:${{1/{Tg}} = {\sum\limits_{i}\quad\left( {\varpi_{i}/{Tg}_{i}} \right)}},$

ω_(i) being the mass fraction of the monomer i in the block underconsideration and Tg_(i) being the glass transition temperature of thehomopolymer of the monomer i.

Unless otherwise indicated, the Tg values indicated for the at least onefirst and second blocks are theoretical Tg values.

The difference between the glass transition temperatures of the at leastone first and second blocks may be generally greater than 10° C., forexample greater than 20° C., and as a further example greater than 30°C.

In one embodiment, the at least one first block may be chosen from:

-   -   a) a block with a Tg of greater than or equal to 40° C.    -   b) a block with a Tg of less than or equal to 20° C.,    -   c) a block with a Tg of between 20 and 40° C.

and the at least one second block is chosen from a block of category a),b) or c) that may be different from the first block.

As used herein, the expression “between . . . and . . . ” is intended todenote a range of values for which the limits mentioned are excluded,and “from . . . to . . . ” and “ranging from . . . to . . . ” areintended to denote a range of values for which the limits are included.

a) Block with a Tg of Greater than or Equal to 40° C.

The block with a Tg of greater than or equal to 40° C. has, for example,a Tg ranging from 40 to 150° C., in another embodiment greater than orequal to 50° C., for example ranging from 50° C. to 120° C., as afurther example, ranging from 50° C. to 100° C., and in a furtherembodiment greater than or equal to 60° C., for example ranging from 60°C. to 120° C.

The block with a Tg of greater than or equal to 40° C. may be ahomopolymer or a copolymer.

In the case where this block is a homopolymer, it may be derived from atleast one monomer wherein a homopolymer prepared from the at least onemonomer has a glass transition temperature of greater than or equal to40° C. This first block may be a homopolymer comprising one type ofmonomer (for which the Tg of the corresponding homopolymer is greaterthan or equal to 40° C.).

In the case where the at least one first block is a copolymer, it may betotally or partially derived from at least one monomer, the nature andconcentration of which are chosen so that the Tg of the resultingcopolymer is greater than or equal to 40° C. The copolymer may comprise,for example:

-   -   monomers wherein the homopolymers prepared from these monomers        have Tg values of greater than or equal to 40° C., for example a        Tg ranging from 40 to 150° C., in one embodiment greater than or        equal to 50° C., for example ranging from 50° C. to 120° C., as        a further example ranging from 50° C. to 100° C. and in another        embodiment greater than or equal to 60° C., for example ranging        from 60° C. to 120° C., and    -   monomers wherein the homopolymers prepared from these monomers        have Tg values of less than 40° C., chosen from monomers with a        Tg of between 20 and 40° C. and/or monomers with a Tg of less        than or equal to 20° C., for example a Tg ranging from −100 to        20° C., in another embodiment less than or equal to 15° C., for        example ranging from −80° C. to 15° C., and in another        embodiment less than or equal to 10° C., for example ranging        from −100° C. to 0° C., and as a further example ranging from        −50° C. to 0° C., as described below.

The monomers whose homopolymers have a glass transition temperature ofgreater than or equal to 40° C. are chosen, for example, from thefollowing monomers, also known as the main monomers:

-   -   methacrylates of formula CH₂═C(CH₃)—COOR₁        -   wherein R₁ is chosen from linear and branched unsubstituted            alkyl groups comprising from 1 to 4 carbon atoms, from            methyl, ethyl, propyl, and isobutyl groups and from C₄ to            C₁₂ cycloalkyl groups,    -   acrylates of formula CH₂═CH—COOR₂        -   wherein R₂ is chosen from C₄ to C₁₂ cycloalkyl groups chosen            from an isobornyl group and a tert-butyl group,            -   (meth)acrylamides of formula:        -   wherein R₇ and R₈, which may be identical or different, each            are chosen from a hydrogen atom, linear and branched C₁ to            C₁₂ alkyl groups such as n-butyl, t-butyl, isopropyl,            isohexyl, isooctyl, and isononyl groups; or R₇ is H and R₈            is a 1,1-dimethyl-3-oxobutyl group,        -   and R′ is chosen from H and methyl. Examples of monomers            that may be mentioned include N-butylacrylamide,            N-t-butylacrylamide, N-isopropylacrylamide,            N,N-dimethylacrylamide and N,N-dibutylacrylamide,            -   and mixtures thereof.

Examples of useful main monomers include methyl methacrylate,isobutyl(meth)acrylate, isobornyl(meth)acrylate, and mixtures thereof.

b) Block with a Tg of Less than or Equal to 20° C.

The block with a Tg of less than or equal to 20° C. has, for example, aTg ranging from −100 to 20° C., in another embodiment less than or equalto 15° C., for example ranging from −80° C. to 15° C., and in anotherembodiment less than or equal to 10° C., for example ranging from −100°C. to 0° C., and as a further example ranging from −50° C. to 0° C.

The block with a Tg of less than or equal to 20° C. may be a homopolymeror a copolymer.

In the case where this block is a homopolymer, it may be derived from atleast one monomer wherein the homopolymers prepared from the at leastone monomer has a glass transition temperature of less than or equal to20° C. This second block may be a homopolymer comprising one type ofmonomer (for which the Tg of the corresponding homopolymer is less thanor equal to 20° C.).

In the case where the block with a Tg of less than or equal to 20° C. isa copolymer, it may be totally or partially derived from at least onemonomer, the nature and concentration of which are chosen so that the Tgof the resulting copolymer is less than or equal to 20° C.

It may comprise, for example

-   -   at least one monomer whose corresponding homopolymer has a Tg of        less than or equal to 20° C., for example a Tg ranging from        −100° C. to 20° C., in another embodiment less than or equal to        15° C., for example ranging from −80° C. to 15° C., and in        another embodiment less than or equal to 10° C., for example        ranging from −100° C. to 0° C. and as a further example ranging        from −50° C. to 0° C., and    -   at least one monomer whose corresponding homopolymer has a Tg of        greater than 20° C., for example monomers with a Tg of greater        than or equal to 40° C., for example a Tg ranging from 40 to        150° C., in another embodiment greater than or equal to 50° C.,        for example ranging from 50° C. to 120° C., as a further example        ranging from 50° C. to 100° C., and in another embodiment        greater than or equal to 60° C., for example ranging from 60° C.        to 120° C. and/or monomers with a Tg of between 20 and 40° C.,        as described above.

In one embodiment, the block with a Tg of less than or equal to 20° C.is a homopolymer.

The monomers whose homopolymer has a Tg of less than or equal to 20° C.may be, for example, chosen from the following monomers, or mainmonomer:

-   -   acrylates of formula CH₂═CHCOOR₃,    -   wherein R₃ is chosen from linear and branched C₁ to C₁₂        unsubstituted alkyl groups, with the exception of the tert-butyl        group, wherein at least one heteroatom chosen from O, N and S is        (are) optionally intercalated,        -   methacrylates of formula CH₂═C(CH₃)—COOR₄,    -   wherein R₄ is chosen from linear and branched C₆ to C₁₂        unsubstituted alkyl groups, wherein at least one heteroatom        chosen from O, N and S is (are) optionally intercalated,        -   vinyl esters of formula R₅—CO—O—CH═CH₂    -   wherein R₅ is chosen from linear and branched C₄ to C₁₂ alkyl        groups,        -   C₄ to C₁₂ alcohol and vinyl alcohols,        -   N—(C₄ to C₁₂)alkyl acrylamides, for example            N-octylacrylamide,        -   and mixtures thereof.

The main monomers for the block with a Tg of less than or equal to 20°C. may be, for example, alkyl acrylates whose alkyl chain contains from1 to 10 carbon atoms, with the exception of the tert-butyl group, chosenfrom methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, andmixtures thereof.

c) Block with a Tg of Between 20 and 40° C.

The block with a Tg of between 20 and 40° C. may be a homopolymer or acopolymer.

In the case where this block is a homopolymer, it may be derived from atleast one monomer (or main monomer) wherein the homopolymers preparedfrom the at least one monomer has a glass transition temperature ofbetween 20 and 40° C. This first block may be a homopolymer comprisingone type of monomer (for which the Tg of the corresponding homopolymerranges from 20° C. to 40° C.).

The at least one monomer whose homopolymer has a glass transitiontemperature of between 20 and 40° C. may be, for example, chosen fromn-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, andisodecylacrylamide.

In the case where the block with a Tg of between 20 and 40° C. is acopolymer, it may be totally or partially derived from at least onemonomer (or main monomer) whose nature and concentration are chosen sothat the Tg of the resulting copolymer is between 20 and 40° C.

The block with a Tg of between 20 and 40° C. may be a copolymer totallyor partially derived from:

-   -   main monomers whose corresponding homopolymer has a Tg of        greater than or equal to 40° C., for example a Tg ranging from        40° C. to 150° C., in another embodiment greater than or equal        to 50° C., for example ranging from 50 to 120° C., as a further        example ranging from 50° C. to 100° C., and in another        embodiment greater than or equal to 60° C., for example ranging        from 60° C. to 120° C., as described above, and/or    -   main monomers whose corresponding homopolymer has a Tg of less        than or equal to 20° C., for example a Tg ranging from −100 to        20° C., in another embodiment less than or equal to 15° C., for        example ranging from −80° C. to 15° C., and in another        embodiment less than or equal to 10° C., for example ranging        from −100° C. to 0° C., and as a further example ranging from        −50° C. to 0° C., as described above,

the at least one monomer may be chosen so that the Tg of the copolymerforming the at least one first block is between 20 and 40° C.

The main monomers may be chosen, for example, from methyl methacrylate,isobornyl acrylate, methacrylate, butyl acrylate, 2-ethylhexyl acrylate,and mixtures thereof.

In one embodiment, the at least one second block with a Tg of less thanor equal to 20° C. is present in an amount ranging from 10% to 85% byweight, in another embodiment from 20% to 70%, and in another embodimentfrom 20% to 50% by weight of the block polymer.

However, each of the at least one first and second blocks may contain insmall proportion at least one constituent monomer of the other at leastone first and second block. Thus, the at least one first block maycontain at least one constituent monomer of the at least one secondblock, and vice versa.

Each of the at least one first and/or second blocks may comprise, inaddition to the at least one monomer indicated above, at least one othermonomer known as an at least one additional monomer, which may bedifferent from the main monomers mentioned above.

The nature and amount of this at least one additional monomer may bechosen so that the at least one first and second block in which they maybe present has the desired glass transition temperature.

This at least one additional monomer may be chosen, for example, from:

a) hydrophilic monomers chosen from:

-   -   ethylenically unsaturated monomers comprising at least one        carboxylic or sulphonic acid function, for example:

acrylic acid, methacrylic acid, crotonic acid, maleic anhydride,itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulphonicacid, vinylbenzoic acid, vinylphosphoric acid, and salts thereof,

-   -   ethylenically unsaturated monomers comprising at least one        tertiary amine function, for example 2-vinylpyridine,        4-vinylpyridine, dimethylaminoethyl methacrylate,        diethylaminoethyl methacrylate,        dimethylaminopropylmethacrylamide, and salts thereof,    -   methacrylates of formula CH₂═C(CH₃)—COOR₆

wherein R₆ may be chosen from linear and branched alkyl groupscomprising from 1 to 4 carbon atoms, chosen from methyl, ethyl, propyland isobutyl groups, the alkyl group being substituted with at least onesubstituent chosen from hydroxyl groups (for instance 2-hydroxypropylmethacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br,I or F), for example trifluoroethyl methacrylate,

-   -   methacrylates of formula CH₂═C(CH₃)—COOR₉,

wherein R₉ may be chosen from linear and branched C₆ to C₁₂ alkyl groupswherein at least one heteroatom chosen from O, N and S is optionallyintercalated, the alkyl group being substituted with at least onesubstituent chosen from hydroxyl groups and halogen atoms (Cl, Br, I orF);

-   -   acrylates of formula CH₂═CHCOOR₁₀,

wherein R₁₀ may be chosen from linear and branched C₁ to C₁₂ alkylgroups substituted with at least one substituent chosen from hydroxyland halogen atoms (Cl, Br, I or F), such as 2-hydroxypropyl acrylate and2-hydroxyethyl acrylate, or

R₁₀ is chosen from (C₁-C₁₂)alkyl-O-POE (polyoxyethylene) with repetitionof the oxyethylene unit 5 to 30 times, for example methoxy-POE, or

R₁₀ is chosen from a polyoxyethylenated group comprising from 5 to 30ethylene oxide units,

b) ethylenically unsaturated monomers comprising at least one siliconatom, chosen from methacryloxypropyltrimethoxysilane andmethacryloxypropyl-tris(trimethylsiloxy)silane,

-   -   and mixtures thereof.

Examples of at least one additional monomer may be, for example, acrylicacid, methacrylic acid, trifluoroethyl methacrylate, and mixturesthereof.

According to an embodiment, the block polymer disclosed herein may be anon-silicone polymer, i.e., a polymer free of silicon atoms.

The at least one additional monomer may be generally present in anamount of less than or equal to 30% by weight, for example from 1% to30% by weight, in another embodiment from 5% to 20% by weight, and forexample from 7% to 15% by weight, relative to the total weight of the atleast one first and/or second blocks.

In one embodiment, each of the first and second blocks comprises atleast one monomer chosen from (meth)acrylic acid esters and(meth)acrylic acid, and mixtures thereof.

In another embodiment, each of the first and second blocks is totallyderived from at least one monomer chosen from acrylic acid,(meth)acrylic acid esters, and (meth)acrylic acid, and mixtures thereof.

In one embodiment, the block polymer disclosed herein is free ofstyrene. “Polymer free of styrene” means that the polymer contains lessthan 10% by weight, relative to the total weight of the polymer, forexample, less than 5% by weight, as a further example less than 2% byweight and as another example less than 1% by weight, or does notcontain at all any styrene monomer including styrene and styrenederivatives such as for instance methylstyrene, chlorostyrene orchloromethylstyrene.

The block polymer disclosed herein may be obtained by free-radicalsolution polymerization according to the following preparation process:

-   -   a portion of the polymerization solvent is introduced into a        suitable reactor and heated until the adequate temperature for        the polymerization is reached (for example between 60 and 120°        C.),    -   once this temperature is reached, the at least one constituent        monomer of the at least one first block are introduced in the        presence of some of the polymerization initiator,    -   after a time T corresponding to a maximum degree of conversion        of 90%, the at least one constituent monomer of the at least one        second block and the rest of the initiator are introduced,    -   the mixture is left to react for a time T′ (ranging from 3 to 6        hours), after which the mixture is cooled to room temperature,    -   the block polymer dissolved in the polymerization solvent is        obtained.

The term “polymerization solvent” means a solvent or a mixture ofsolvents. The polymerization solvent may be chosen, for example, fromethyl acetate, butyl acetate, alcohols chosen from isopropanol andethanol, aliphatic alkanes chosen from isododecane, and mixturesthereof. For example, the polymerization solvent is a mixture of butylacetate and isopropanol or isododecane.

FIRST EMBODIMENT

According to a first embodiment, the block polymer comprises at leastone first block with a Tg of greater than or equal to 40° C., asdescribed above in a) and at least one second block with a Tg of lessthan or equal to 20° C., as described above in b).

For example, the at least one first block with a Tg of greater than orequal to 40° C. may be a copolymer derived from at least one monomerwherein the homopolymer prepared from at least one monomer has a glasstransition temperature of greater than or equal to 40° C., for examplethe at least one monomer described above.

The at least one second block with a Tg of less than or equal to 20° C.may be a homopolymer derived from at least one monomer wherein thehomopolymer prepared from at least one monomer has a glass transitiontemperature of less than or equal to 20° C., for example the at leastone monomer described above.

the at least one first block with a Tg of greater than or equal to 40°C. is present in an amount ranging from 20% to 90%, for example from 30%to 80%, and as a further example from 50% to 70% by weight of the blockpolymer. For example, the at least one second block with a Tg of lessthan or equal to 20° C. is present in an amount ranging from 5% to 75%,for example from 15% to 50%, and in a further example from 25% to 45% byweight of the block polymer.

Thus, according to a first variant, the block polymer disclosed hereinmay comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example having a Tg ranging from 70 to 110° C.,        which may be a methyl methacrylate/acrylic acid copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from 0 to 20° C., which may be a methyl        acrylate homopolymer, and    -   at least one intermediate segment which may be a methyl        methacrylate/acrylic acid/methyl acrylate copolymer.

According to a second variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 70 to 100° C., which may be a        methyl methacrylate/acrylic acid/trifluoroethyl methacrylate        copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from 0 to 20° C., which may be a methyl        acrylate homopolymer, and    -   at least one intermediate segment which may be a methyl        methacrylate/acrylic acid/methyl acrylate/trifluoroethyl        methacrylate random copolymer.

According to a third variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 0 to 20° C., which may be an        isobornyl acrylate/isobutyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −85 to −55° C., which may be a        2-ethylhexyl acrylate homopolymer, and    -   at least one intermediate segment, which may be an isobornyl        acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random        copolymer.

According to a fourth variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 85 to 115° C., which may be an        isobornyl acrylate/methyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −85 to −55° C., which may be a        2-ethylhexyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/methyl methacrylate/2-ethylhexyl acrylate random        copolymer.

According to a fifth variant, the block polymer disclosed herein maycomprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 95 to 125° C., which may be an        isobornyl acrylate/isobornyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −85 to −55° C., which may be a        2-ethylhexyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/isobornyl methacrylate/2-ethylhexyl acrylate random        copolymer.

According to a sixth variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 85 to 115° C., which may be an        isobornyl methacrylate/isobutyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −35 to −5° C., which may be an        isobutyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        methacrylate/isobutyl acrylate random copolymer.

According to a seventh variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 95 to 125° C., which may be an        isobornyl acrylate/isobornyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −35 to −5° C., which may be an        isobutyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/isobornyl methacrylate/isobutyl acrylate random        copolymer.

According to an eighth variant, the block polymer may comprise:

-   -   at least one first block with a Tg of greater than or equal to        40° C., for example ranging from 60 to 90° C., which may be an        isobornyl acrylate/isobutyl methacrylate copolymer,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −35 to −5° C., which may be an        isobutyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/isobutyl methacrylate/isobutyl acrylate random        copolymer.

The examples that follow illustrate, in a non-limiting manner, blockpolymers corresponding to the first embodiment disclosed above.

The amounts are expressed in grams.

Example 1 Preparation of a poly(methyl methacrylate)/acrylic acid/methylacrylate)polymer

100 g of butyl acetate were introduced into a 1 liter reactor and thetemperature was then raised so as to pass from room temperature (25° C.)to 90° C. in 1 hour. 180 g of methyl methacrylate, 30 g of acrylic acid,40 g of butyl acetate, 70 g of isopropanol and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour.

90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were thenintroduced into the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and then diluted with105 g of butyl acetate and 45 g of isopropanol, and the mixture was thencooled.

A solution containing 40% polymer active material in a butylacetate/isopropanol mixture was obtained.

A block polymer comprising a poly(methyl methacrylate/acrylic acid)first block with a Tg of 100° C., a polymethyl acrylate second blockwith a Tg of 10° C. and an intermediate segment which was a methylmethacrylate/acrylic acid/polymethyl acrylate random polymer wasobtained.

This polymer had a weight-average mass of 52 000 and a number-averagemass of 18 000, i.e., a polydispersity index I of 2.89.

Example 2 Preparation of a poly(methyl methacrylate)/acrylic acid/methylmethacrylate)polymer

100 g of butyl acetate were introduced into a 1 liter reactor and thetemperature was then raised so as to pass from room temperature (25° C.)to 90° C. in 1 hour. 150 g of methyl methacrylate, 30 g of acrylic acid,30 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX®141 from Akzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour.

90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were thenintroduced into the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and then diluted with105 g of butyl acetate and 45 g of isopropanol, and the mixture was thencooled.

A solution containing 40% polymer active material in a butylacetate/isopropanol mixture was obtained.

A block polymer comprising a poly(acrylic acid/methyl methacrylate)first block with a Tg of 80° C., a polymethyl acrylate second block witha Tg of 10° C. and an intermediate segment which was an acrylicacid/methyl acrylate/polymethyl acrylate random polymer was obtained.

This block polymer had a weight-average mass of 50 000 and anumber-average mass of 17 000, i.e., a polydispersity index I of 2.95.

Example 3 Preparation of a poly(acrylic acid/methyl acrylate/polymethylacrylate/trifluoroethyl methacrylate)polymer

100 g of butyl acetate were introduced into a 1 liter reactor and thetemperature was then raised so as to pass from room temperature (25° C.)to 90° C. in 1 hour. 120 g of methyl methacrylate, 30 g of acrylic acid,60 g of trifluoroethyl methacrylate, 40 g of butyl acetate, 70 g ofisopropanol and 1.8 g of2,5-bis(2-ethyl-hexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour.

90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were thenintroduced into the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and then diluted with105 g of butyl acetate and 45 g of isopropanol, and the mixture was thencooled.

A solution containing 40% polymer active material in a butylacetate/isopropanol mixture was obtained.

A block polymer comprising a poly(acrylic acid/methylmethacrylate/trifluoroethyl methacrylate) first block with a Tg of 85°C., a polymethyl acrylate second block with a Tg of 10° C. and anintermediate segment which was an acrylic acid/methylacrylate/polymethyl acrylate/trifluoroethyl methacrylate random polymerwas obtained.

This block polymer had a weight-average mass of 53 000 and anumber-average mass of 17 500, i.e., a polydispersity index I of 3.03.

Example 4 Preparation of a poly(isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 120 g of isobornyl acrylate, 90 g of isobutylmethacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/isobutylmethacrylate) first block with a Tg of 80° C., a poly-2-ethylhexylacrylate second block with a Tg of −70° C. and an intermediate segmentwhich was an isobornyl acrylate/isobutyl methacrylate/2-ethylhexylacrylate random polymer was obtained.

This block polymer had a weight-average mass of 77 000 and anumber-average mass of 19 000, i.e., a polydispersity index I of 4.05.

Example 5 Preparation of a poly(isobornyl acrylate/methylmethacrylate/2-ethylhexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 150 g of isobornyl acrylate, 60 g of methylmethacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/methylmethacrylate) first block with a Tg of 100° C., a poly-2-ethylhexylacrylate second block with a Tg of −70° C. and an intermediate segmentwhich was an isobornyl acrylate/methyl methacrylate/2-ethylhexylacrylate random polymer was obtained.

This block polymer had a weight-average mass of 76 500 and anumber-average mass of 22 000, i.e., a polydispersity index I of 3.48.

Example 6 Preparation of a poly(isobornyl acrylate/methylmethacrylate/2-ethylhexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 90 g of isobornyl acrylate, 60 g of methylmethacrylate, 50 g of isododecane and 1.5 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

150 g of 2-ethylhexyl acrylate, 150 g of isododecane and 1.5 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/methylmethacrylate) first block with a Tg of 100° C., a poly-2-ethylhexylacrylate second block with a Tg of −70° C. and an intermediate segmentwhich was an isobornyl acrylate/methyl methacrylate/2-ethylhexylacrylate random polymer was obtained.

This block polymer had a weight-average mass of 76 500 and anumber-average mass of 22 000, i.e., a polydispersity index I of 3.48.

Example 7 Preparation of a poly(isobornyl acrylate/isobornylmethacrylate/2-ethyl hexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 105 g of isobornyl acrylate, 105 g ofisobornyl methacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/isobornylmethacrylate) first block with a Tg of 110° C., a poly-2-ethylhexylacrylate second block with a Tg of −70° C. and an intermediate segmentwhich was an isobornyl acrylate/isobornyl methacrylate/2-ethylhexylacrylate random polymer was obtained.

This block polymer had a weight-average mass of 103 900 and anumber-average mass of 21 300, i.e., a polydispersity index I of 4.89.

Example 8 Preparation of a poly(isobornyl methacrylate/isobutylmethacrylate/isobutyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 120 g of isobornyl methacrylate, 90 g ofisobutyl methacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl methacrylate/isobutylmethacrylate) first block with a Tg of 95° C., a polyisobutyl acrylatesecond block with a Tg of −20° C. and an intermediate segment which wasan isobornyl methacrylate/isobutyl methacrylate/isobutyl acrylate randompolymer was obtained.

This block polymer had a weight-average mass of 100 700 and anumber-average mass of 20 800, i.e., a polydispersity index I of 4.85.

Example 9 Preparation of a poly(isobornyl acrylate/isobornylmethacrylate/isobutyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 105 g of isobornyl acrylate, 105 g ofisobornyl methacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/isobornylmethacrylate) first block with a Tg of 110° C., a polyisobutyl acrylatesecond block with a Tg of −20° C. and an intermediate segment which wasan isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate randompolymer was obtained.

This block polymer had a weight-average mass of 151 000 and anumber-average mass of 41 200, i.e. a polydispersity index I of 3.66.

Example 10 Preparation of a poly(isobornyl acrylate/isobutylmethacrylate/isobutyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 120 g of isobornyl acrylate, 90 g of isobutylmethacrylate, 110 g of isododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 30 minutes.

The mixture was maintained at 90° C. for 3 hours and was then cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/isobutylmethacrylate) first block with a Tg of 75° C., a polyisobutyl acrylatesecond block with a Tg of −20° C. and an intermediate segment which wasan isobornyl acrylate/isobutyl methacrylate/isobutyl acrylate randompolymer was obtained.

This block polymer had a weight average mass of 144 200 and anumber-average mass of 49 300, i.e. a polydispersity index I of 2.93.

SECOND EMBODIMENT

According to a second embodiment, the block polymer disclosed hereincomprises at least one first block having a glass transition temperature(Tg) of between 20 and 40° C., in accordance with the blocks describedin c) and at least one second block having a glass transitiontemperature of less than or equal to 20° C., as described above in b) ora glass transition temperature of greater than or equal to 40° C., asdescribed in a) above.

The at least one first block with a Tg of between 20 and 40° C. rangesis present in an amount from 10% to 85% by weight of the polymer, forexample from 30% to 80%, and as a further example from 50% to 70%.

When the at least one second block is a block with a Tg of greater thanor equal to 40° C., it may be, for example present in an amount rangingfrom 10% to 85% by weight, for example from 20% to 70%, and as a furtherexample from 30% to 70% by weight of the block polymer.

When the at least one second block is a block with a Tg of less than orequal to 20° C., it may be, for example, present in an amount rangingfrom 10% to 85% by weight, for example from 20% to 70%, and as a furtherexample from 20% to 50% by weight of the block polymer.

For example, the at least one first block with a Tg of between 20 and40° C. may be a copolymer derived from at least one monomer wherein thecorresponding homopolymer has a Tg of greater than or equal to 40° C.,and from at least one monomer wherein the corresponding homopolymer hasa Tg of less than or equal to 20° C.

The at least one second block with a Tg of less than or equal to 20° C.or with a Tg of greater than or equal to 40° C. may be a homopolymer.

Thus, according to a first variant of this second embodiment, the blockpolymer may comprise:

-   -   at least one first block with a Tg of between 20 and 40° C., for        example with a Tg of 25 to 39° C., which may be a copolymer        comprising at least one methyl acrylate monomer, at least one        methyl methacrylate monomer, and at least one acrylic acid        monomer,    -   at least one second block with a Tg of greater than or equal to        40° C., for example ranging from 85 to 125° C., which may be a        homopolymer composed of methyl methacrylate monomers, and    -   at least one intermediate segment comprising at least one methyl        acrylate, methyl methacrylate monomer, and    -   at least one intermediate segment comprising methyl        methacrylate, at least one acrylic acid monomer, and at least        one methyl acrylate monomer.

According to a second variant of this second embodiment, the blockpolymer may comprise:

-   -   at least one first block with a Tg of between 20 and 40° C., for        example with a Tg of 21 to 39° C., which may be a copolymer        comprising isobornyl acrylate/isobutyl methacrylate/2-ethylhexyl        acrylate,    -   at least one second block with a Tg of less than or equal to 20°        C., for example ranging from −65 to −35° C., which may be a        methyl methacrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/isobutyl methacrylate/2-ethylhexyl acrylate random        copolymer.

According to a third variant of this second embodiment, the blockpolymer may comprise:

-   -   at least one first block with a Tg of between 20 and 40° C., for        example with a Tg from 21 to 39° C., which may be an isobornyl        acrylate/methyl acrylate/acrylic acid copolymer,    -   at least one second block with a Tg of greater than or equal to        40° C., for example ranging from 85 to 115° C., which may be an        isobornyl acrylate homopolymer, and    -   at least one intermediate segment which may be an isobornyl        acrylate/methyl acrylate/acrylic acid random copolymer.

As a non-limiting illustration, the block polymers corresponding to thissecond embodiment may be prepared as follows.

Example 11 Preparation of a poly(butyl methacrylate/butylacrylate)polymer

100 g of butyl acetate were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 210 g of butyl methacrylate, 110 g of butylacetate and 1.8 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane(TRIGONOX® 141 from Akzo Nobel) were then added, at 90° C. and over 1hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

90 g of butyl acrylate, 90 g of isopropanol and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and was then dilutedwith 105 g of butyl acetate and 45 g of isopropanol, and then cooled.

A solution containing 40% of polymer active material in a butylacetate/isopropanol mixture was obtained.

A block polymer comprising a polybutyl methacrylate first block with aTg of 25° C., a polybutyl acrylate second block with a Tg of −50° C. andan intermediate segment which was a butyl methacrylate/butyl acrylaterandom polymer was obtained.

This block polymer had a weight-average mass of 57 560 and anumber-average mass of 19 025, i.e. a polydispersity index I of 3.03.

Example 12 Preparation of a poly(methyl methacrylate/methylacrylate/acrylic acid)polymer

100 g of butyl acetate were introduced into a 1 liter reactor and thetemperature was then raised so as to pass from room temperature (25° C.)to 90° C. over 1 hour. 50.4 g of methyl methacrylate, 21 g of acrylicacid, 138.6 g of methyl acrylate, 40 g of butyl acetate, 70 g ofisopropanol and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour.

90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanoland 1.2 g of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were thenintroduced into the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and then diluted with105 g of butyl acetate and 45 g of isopropanol, and cooled.

A solution containing 40% polymer active material in a butylacetate/isopropanol mixture was obtained.

The block polymer obtained comprises a poly(methyl acrylate/methylmethacrylate/acrylic acid) first block with a Tg of 35° C., apoly(methyl methacrylate) second block with a Tg of 100° C. and anintermediate segment which was a methyl methacrylate/acrylicacid/polymethyl acrylate random polymer.

Example 13 Preparation of a poly(isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 105 g of isobornyl acrylate, 50.4 g ofisobutyl methacrylate, 54.6 g of 2-ethylhexyl acrylate, 110 g ofisododecane and 1.8 g of2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour. This mixture wasmaintained at 90° C. for 1 hour 30 minutes.

90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and was then dilutedand cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

The block polymer obtained comprises a poly(isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate) first block with a Tg of 35° C., apoly(2-ethylhexyl acrylate) second block with a Tg of −50° C. and anintermediate segment which was an isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate random polymer.

Example 14 Preparation of a poly(isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 54 g of isobornyl acrylate, 75.6 g ofisobutyl methacrylate, 50.4 g of 2-ethylhexyl acrylate, 110 g ofisododecane and 1.8 g of2,5-bis(2-ethylhexanoyl-peroxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour. The mixture wasmaintained at 90° C. for 1 hour 30 minutes.

120 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethyl hexane were then introducedinto the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and was then dilutedand cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A block polymer comprising a poly(isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate) first block with a Tg of 25° C., apoly(2-ethylhexyl acrylate) second block with a Tg of −50° C. and anintermediate segment which was an isobornyl acrylate/isobutylmethacrylate/2-ethylhexyl acrylate random polymer was obtained.

Example 15 Preparation of a poly(isobornyl acrylate/acrylic acid/methylacrylate)polymer

100 g of isododecane were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 90° C. over 1 hour. 210 g of isobornyl acrylate, 110 g ofisododecane and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour 30 minutes.

18 g of isobornyl acrylate, 71.1 g of methyl acrylate, 0.9 g of acrylicacid, 90 g of isododecane and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 90° C. and over 1 hour.

The mixture was maintained at 90° C. for 3 hours and was then dilutedand cooled.

A solution containing 50% polymer active material in isododecane wasobtained.

A polymer comprising a poly(isobornyl acrylate/methyl acrylate/acrylicacid) first block with a Tg of 25° C., a polyisobornyl acrylate secondblock with a Tg of 100° C. and an intermediate segment which was an(isobornyl acrylate/methyl acrylate/acrylic acid) random polymer wasobtained.

The following polymer was prepared:

Example 16 Preparation of a poly(methyl methacrylate/methylacrylate/acrylic acid)polymer

210 g of ethyl acetate were introduced into a 1 liter reactor and thetemperature was then increased so as to pass from room temperature (25°C.) to 78° C. over 1 hour. 54 g of methyl methacrylate, 21 g of acrylicacid, 135 g of methyl acrylate and 1.8 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX® 141 fromAkzo Nobel) were then added, at 78° C. and over 1 hour.

The mixture was maintained at 90° C. for 1 hour.

90 g of methyl methacrylate, 90 g of ethyl acetate and 1.2 g of2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane were then introducedinto the above mixture, still at 78° C. and over 1 hour.

The mixture was maintained at 78° C. for 3 hours and was then dilutedwith 150 g of ethyl acetate and cooled.

A solution containing 40% polymer active material in ethyl acetate wasobtained.

The block polymer obtained comprises a poly(methyl acrylate/methylmethacrylate/acrylic acid) first block with a Tg of 35° C., apoly(methyl methacrylate) second block with a Tg of 100° C. and anintermediate segment which was a methyl methacrylate/acrylicacid/polymethyl acrylate random polymer.

This block polymer had a weight-average mass of 141 000 and anumber-average mass of 50 000, i.e. a polydispersity index I of 2.82.

Disclosed herein are also cosmetic compositions comprising at least oneblock polymer of specific structure as described above.

Generally, these compositions contain from 0.1% to 60% by weight ofactive material (or solids) of the block polymer disclosed herein, forexample from 0.5% to 50% by weight, and as a further example from 1% to40% by weight.

These cosmetic compositions comprise, besides the block polymers, aphysiologically acceptable medium, i.e., a medium that is compatiblewith keratin materials, for example the skin, the hair, the eyelashes,the eyebrows, and the nails.

The physiologically acceptable medium generally comprises aphysiologically acceptable suitable solvent.

The composition may thus comprise a hydrophilic medium comprising wateror a mixture of water and hydrophilic organic solvent(s), for examplealcohols and for example linear and branched lower monoalcoholscontaining from 2 to 5 carbon atoms, for example ethanol, isopropanol,or n-propanol, and polyols, for example glycerol, diglycerol, propyleneglycol, sorbitol or pentylene glycol, and polyethylene glycols, orhydrophilic C₂ ethers and C₂-C₄ aldehydes.

The water or the mixture of water and hydrophilic organic solvents maybe present in the composition in an amount ranging from 0.1% to 99% byweight, and for example from 10% to 80% by weight relative to the totalweight of the composition.

The composition may comprise, besides the block polymer described above,at least one additional polymer such as a film-forming polymer. Asdefined herein, the term “film-forming polymer” means a polymer that maybe capable, by itself or in the presence of an auxiliary film-formingagent, of forming a continuous film that adheres to a support, forexample to keratin materials.

Among the film-forming polymers that may be used in the compositiondisclosed herein, mention may be made of synthetic polymers, offree-radical type or of polycondensate type, and polymers of naturalorigin, and mixtures thereof. Film-forming polymers that may bementioned, for example, include acrylic polymers, polyurethanes,polyesters, polyamides, polyureas and cellulose-based polymers, forexample nitrocellulose.

The composition may also comprise a fatty phase comprising fattysubstances that are liquid at room temperature (in general 25° C.)and/or of fatty substances that are solid at room temperature, chosenfrom waxes, pasty fatty substances, gums, and mixtures thereof. Thesefatty substances may be of animal, plant, mineral or synthetic origin.This fatty phase may also contain lipophilic organic solvents.

As fatty substances that are liquid at room temperature, often referredto as oils, which may be used herein, mention may be made of:hydrocarbon-based oils of animal origin for example perhydrosqualene;hydrocarbon-based plant oils for example liquid triglycerides of fattyacids of 4 to 10 carbon atoms, for example heptanoic or octanoic acidtriglycerides, or alternatively sunflower oil, maize oil, soybean oil,grapeseed oil, sesame seed oil, apricot oil, macadamia oil, castor oil,avocado oil, caprylic/capric acid triglycerides, jojoba oil, karitebutter, linear or branched hydrocarbons of mineral or synthetic origin,chosen from liquid paraffin and derivatives thereof, petroleum jelly,polydecenes, hydrogenated polyisobutene for example parleam; syntheticesters and ethers, for example of fatty acids, for example purcellinoil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecylstearate, 2-octyldodecyl erucate, isostearyl isostearate; hydroxylatedesters, for example isostearyl lactate, octyl hydroxystearate,octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate,and fatty alcohol heptanoates, octanoates and decanoates; polyol esters,for example propylene glycol dioctanoate, neopentyl glycol diheptanoateand diethylene glycol diisononanoate; and pentaerythritol esters; fattyalcohols containing from 12 to 26 carbon atoms, for exampleoctyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanoland oleyl alcohol; partially hydrocarbon-based fluoro oils and/orfluorosilicone oils; silicone oils, chosen from volatile andnon-volatile, linear and cyclic polymethylsiloxanes (PDMSs), which areliquid or pasty at room temperature, for example cyclomethicones,dimethicones, optionally comprising a phenyl group, for example phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes,diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyldimethicones and polymethylphenylsiloxanes; and mixtures thereof.

These oils may be present in an amount ranging from 0.01% to 90% and forexample from 0.1% to 85% by weight relative to the total weight of thecomposition.

A “pasty fatty substance” is a viscous product comprising a liquidfraction and a solid fraction. As defined herein, the term “pasty fattysubstance” is understood to mean fatty substances having a melting pointranging from 20° C. to 55° C., such as from 25° C. to 45° C., and/or aviscosity at 40° C. ranging from 0.1 to 40 Pa·s (1 to 400 poises), suchas from 0.5 to 25 Pa·s, measured with a Contraves TV or Rhéomat 80equipped with a rotor rotating at 60 Hz. The person skilled in the artcan choose, from the MSr3 and MSr4 rotors, on the basis of his generalknowledge, the rotor which makes it possible to measure the viscosity,so as to be able to carry out the measurement of the pasty compoundtested.

The melting point values of the pasty fatty substances correspond, asdisclosed herein, to the melting peak measured by the “Dynamic ScanningColorimetry” method with a rising temperature of 5 or 10° C./min.

The composition disclosed herein may contain at least one pasty fattysubstance. For example, the at least one pasty fatty substance may bechosen from hydrocarbonaceous compounds (mainly comprising carbon andhydrogen atoms and optionally ester groups), optionally of polymer type;they can also be chosen from silicone and/or fluorinated compounds; theycan also be provided in the form of a mixture of hydrocarbonaceousand/or silicone and/or fluorinated compounds. In the case of a mixtureof various pasty fatty substances, predominantly hydrocarbonaceous pastycompounds may be used.

In one embodiment, the at least one pasty fatty compound is chosen fromlanolins and lanolin derivatives, such as acetylated lanolins oroxypropylenated lanolins or isopropyl lanolate, having a viscosity of 18to 21 Pa·s, such as 19 to 20.5 Pa·s, and/or a melting point of 30 to 55°C., and their mixtures. The at least one pasty fatty substance may alsobe chosen from esters of fatty acids or of fatty alcohols, such as thosehaving 20 to 65 carbon atoms (melting point of the order of 20 to 35° C.and/or viscosity at 40° C. ranging from 0.1 to 40 Pa·s), such astri-isostearyl or cetyl citrate; arachidyl propionate; poly(vinyllaurate); cholesterol esters, such as triglycerides of vegetable origin,for example hydrogenated vegetable oils, viscous polyesters, such aspoly(12-hydroxystearic acid), and their mixtures. For example, the atleast one pasty fatty substance, as a triglyceride of vegetable origin,may be chosen from derivatives of hydrogenated castor oil, such as“Thixinr” from Rheox.

Mention may also be made of silicone pasty fatty substances, such aspolydimethylsiloxanes (PDMSs) having pendent chains of the alkyl oralkoxy type having from 8 to 24 carbon atoms and a melting point of20-55° C., such as stearyl dimethicones, for example those sold by DowCorning under the trade names of DC2503 and D 25514, and their mixtures.

The at least one pasty fatty substance may be present in the disclosedcomposition in an amount ranging from 0.5 to 60% by weight with respectto the total weight of the composition, for example from 2 to 45% byweight and as a further example from 5 to 30% by weight.

The composition disclosed herein may also comprise at least onecosmetically acceptable (acceptable tolerance, toxicology and feel)organic solvent. The at least one solvent may be generally present in anamount ranging from 0 to 90%, for example from 0.1 to 90%, as a furtherexample from 10% to 90%, and as another example from 30% to 90% byweight, relative to the total weight of the composition.

As solvents that may be used in the composition disclosed herein,mention may be made, besides the hydrophilic organic solvents mentionedabove, of ketones that are liquid at room temperature chosen from methylethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone,cyclohexanone and acetone; propylene glycol ethers that are liquid atroom temperature, chosen from propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, and dipropylene glycolmono-n-butyl ether; short-chain esters (containing from 3 to 8 carbonatoms in total), chosen from ethyl acetate, methyl acetate, propylacetate, n-butyl acetate, and isopentyl acetate; ethers that are liquidat room temperature, chosen from diethyl ether, dimethyl ether, anddichlorodiethyl ether; alkanes that are liquid at room temperature,chosen from decane, heptane, dodecane, isododecane and cyclohexane;aromatic cyclic compounds that are liquid at room temperature, chosenfrom toluene and xylene; aldehydes that are liquid at room temperature,chosen from benzaldehyde and acetaldehyde, and mixtures thereof.

As defined herein, the term “wax” means a lipophilic compound that issolid at room temperature (25° C.), which undergoes a reversiblesolid/liquid change of state, and which has a melting point of greaterthan or equal to 30° C., which may be up to 120° C.

By bringing the wax to the liquid state (melting), it may be possible tomake it miscible with the oils possibly present and to form amicroscopically homogeneous mixture, but, on returning the temperatureof the mixture to room temperature, recrystallization of the wax may beobtained in the oils of the mixture. The melting point of the wax may bemeasured using a differential scanning calorimeter (DSC), for examplethe calorimeter sold under the name DSC 30 by the company Mettler.

The wax may also have a hardness ranging from 0.05 MPa to 15 MPa and forexample ranging from 6 MPa to 15 MPa. The hardness may be determined bymeasuring the compressive force, measured at 20° C. using thetexturometer sold under the name TA-XT2i by the company Rheo, equippedwith a stainless-steel cylinder 2 mm in diameter travelling at ameasuring speed of 0.1 mm/second and penetrating the wax to apenetration depth of 0.3 mm.

The waxes may be hydrocarbon-based waxes, fluoro waxes and/or siliconewaxes and may be of plant, mineral, animal and/or synthetic origin. Forexample, the waxes have a melting point of greater than 25° C. and forexample greater than 45° C.

As waxes that may be used in the composition disclosed herein, mentionmay be made of beeswax, carnauba wax or candelilla wax, paraffin,microcrystalline waxes, ceresin or ozokerite, synthetic waxes, forinstance polyethylene waxes or Fischer-Tropsch waxes, and siliconewaxes, for instance alkyl or alkoxy dimethicones containing from 16 to45 carbon atoms.

The gums useful herein are generally polydimethylsiloxanes (PDMSs) ofhigh molecular weight or cellulose gums or polysaccharides.

The nature and amount of the solid substances depend on the desiredmechanical properties and textures. As a guide, the composition maycontain from 0 to 50% by weight and for example from 1% to 30% by weightof waxes relative to the total weight of the composition.

The polymer disclosed herein may be combined with at least one auxiliaryfilm-forming agent. Such a film-forming agent may be chosen from anycompound known to those skilled in the art as being capable ofsatisfying the desired function, and may be chosen for example fromplasticizers and coalescers.

The composition disclosed herein may also comprise at least one dyestuffchosen from water-soluble dyes and pulverulent dyestuffs, for examplepigments, nacres and flakes that are well known to those skilled in theart. The dyestuffs may be present in the composition in an amountranging from 0.01% to 50% by weight and for example from 0.01% to 30% byweight relative to the total weight of the composition.

The term “pigments” should be understood as meaning white or colored,mineral or organic particles of any shape, which are insoluble in thephysiological medium and which are intended to color the composition.

The term “nacres” should be understood as meaning iridescent particlesof any shape, produced for example by certain mollusks in their shell,or alternatively synthesized.

The pigments may be white or colored, and mineral and/or organic. Amongthe mineral pigments that may be mentioned are titanium dioxide,optionally surface-treated, zirconium oxide or cerium oxide, and alsozinc oxide, iron oxide (black, yellow or red) or chromium oxide,manganese violet, ultramarine blue, chromium hydrate and ferric blue,and metal powders, for instance aluminium powder or copper powder. Amongthe organic pigments that may be mentioned are carbon black, pigments ofD & C type, and lakes based on cochineal carmine or on barium,strontium, calcium or aluminium.

Mention may also be made of pigments with an effect, chosen fromparticles comprising a natural or synthetic, organic or mineralsubstrate, for example glass, acrylic resins, polyester, polyurethane,polyethylene terephthalate, ceramics and aluminas, the substrate beinguncoated or coated with metal substances, for example aluminium, gold,silver, platinum, copper or bronze, or with metal oxides, for exampletitanium dioxide, iron oxide or chromium oxide, and mixtures thereof.

The nacreous pigments may be chosen from white nacreous pigments chosenfrom mica coated with titanium or with bismuth oxychloride, colorednacreous pigments chosen from titanium mica coated with iron oxides,titanium mica coated for example with ferric blue or chromium oxide,titanium mica coated with an organic pigment of the above-mentionedtype, and also nacreous pigments based on bismuth oxychloride.Interference pigments, for example liquid-crystal pigments or multilayerpigments, may also be used.

The water-soluble dyes may be, for example, beetroot juice or methyleneblue.

The composition disclosed herein may also comprise at least one filler,for example in an amount ranging from 0.01% to 50% by weight and forexample ranging from 0.01% to 30% by weight, relative to the totalweight of the composition. The term “fillers” should be understood asmeaning colorless or white, mineral or synthetic particles of any shape,which may be insoluble in the medium of the composition, irrespective ofthe temperature at which the composition is manufactured. The at leastone filler serves for example to modify the rheology or the texture ofthe composition.

The at least one filler may be mineral or organic in any form,platelet-shaped, spherical or oblong, irrespective of thecrystallographic form (for example leaflet, cubic, hexagonal,orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin,polyamide (NYLON®) powders (ORGASOL® from Atochem), poly-β-alaninepowder and polyethylene powder, powders of polytetrafluoroethylenepolymers (TEFLON®), lauroyllysine, starch, boron nitride, hollow polymermicrospheres such as those of polyvinylidene chloride/acrylonitrile, forinstance EXPANCEL® (Nobel Industrie) or acrylic acid copolymers(POLYTRAP® from the company Dow Corning) and silicone resin microbeads(for example TOSPEARLS® from Toshiba), elastomeric polyorganosiloxaneparticles, precipitated calcium carbonate, magnesium carbonate,magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres(SILICA BEADS® from Maprecos), glass or ceramic microcapsules, and metalsoaps derived from organic carboxylic acids containing from 8 to 22carbon atoms and for example from 12 to 18 carbon atoms, for examplezinc, magnesium or lithium stearate, zinc laurate or magnesiummyristate.

The composition disclosed herein may also contain ingredients commonlyused in cosmetics, such as vitamins, thickeners, trace elements,softeners, sequestering agents, fragrances, acidifying or basifyingagents, preserving agents, sunscreens, surfactants, antioxidants, agentsfor preventing hair loss, antidandruff agents and propellants, ormixtures thereof.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compound(s), and/or the amountthereof, so that the advantageous properties of the correspondingcomposition disclosed herein are not, or are not substantially,adversely affected by the envisaged addition.

The composition disclosed herein, for example, be in the form of asuspension, a dispersion, a solution, a gel, an emulsion, for example anoil-in-water (O/W) emulsion, a water-in-oil (W/O) emulsion or a multipleemulsion (W/O/W or polyol/O/W or O/W/O emulsion), in the form of acream, a mousse, a dispersion of vesicles, for example of ionic ornonionic lipids, a two-phase or multi-phase lotion, a spray, a powder, apaste, for example a soft paste (for example a paste with a dynamicviscosity at 25° C. of about from 0.1 to 40 Pa·s under a shear rate of200 s⁻¹, after measurement for 10 minutes in cone/plate geometry). Thecomposition may be anhydrous; for example, it may be an anhydrous paste.

A person skilled in the art may select the appropriate presentationform, and also the method for preparing it, on the basis of his generalknowledge, taking into account firstly the nature of the constituentsused, for example their solubility in the support, and secondly theintended application for the composition.

The composition disclosed herein may be a makeup composition, forexample complexion products (foundations), makeup rouges, eyeshadows,lipcare products, concealer products, blushers, mascaras, eyeliners,eyebrow makeup products, lip pencils, eye pencils, nailcare products,for example nail varnishes, body makeup products, and hair makeupproducts (mascara).

When the composition disclosed herein is a complexion product, it maycomprise a block polymer according to the first embodiment describedabove, such as a polymer comprising at least one first block having a Tgranging from 50° C. to 100° C. and at least one second block having a Tgranging from −100° C. to 0° C. In one embodiment, the block polymer fora complexion product is chosen among the block polymers described in thethird and eighth variants of the first embodiment, as described above.

The composition disclosed herein may also be a care product for body andfacial skin, for example an antisun product or a skin coloring product(for example a self-tanning product).

The composition disclosed herein may also be a haircare product, forexample for holding the hairstyle or shaping the hair. The haircompositions are chosen from shampoos, hair setting gels, hair settinglotions, blow-drying lotions, fixing compositions, and stylingcompositions.

The examples that follow illustrate, in a non-limiting manner, thecompositions comprising the polymer disclosed herein.

The amounts are expressed in grams.

Example 17 Nail Varnish

A nail varnish having the composition below was prepared: Polymer ofExample 1 23.8 g AM Butyl acetate 24.99 g Isopropanol 10.71 g Hexyleneglycol 2.5 g DC Red 7 Lake 1 g Hectorite modified withstearyldimethylbenzylammonium 1.3 g chloride (Bentone ® 27V fromElementis) Ethyl acetate qs 100

After application to the nails, this varnish was considered as havinggood staying power and impact strength properties.

Example 18 Mascara Composition

A mascara having the composition below was prepared: Beeswax 8 gParaffin wax 3 g Carnauba wax 6 g Hectorite modified with 5.3 gdistearyldimethylbenzylammonium chloride (Bentone ® 38V from Elementis)Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer of Example 412 g AM Isododecane qs 100

The staying power of the mascara film, after application to theeyelashes, was considered as being very satisfactory.

Example 19 Mascara Composition

A mascara having the composition below was prepared: Beeswax 8 gParaffin wax 3 g Carnauba wax 6 g Hectorite modified withdistearyldimethylbenzylammonium 5.3 g chloride (Bentone ® 38V fromElementis) Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer ofExample 7 12 g AM Isododecane qs 100

The staying power of the mascara film, after application to theeyelashes, was considered as being very satisfactory.

Example 20 Lipstick in Stick Form

The lipstick composition below is prepared: Polyethylene wax 15% Polymerof Example 5 10% AM Hydrogenated polyisobutene (Parleam from Nippon OilFats) 26% Isododecane qs 100 Pigments 8.6% 

The film of composition obtained after application to the lips showsgood staying power properties.

Example 21 W/O Foundation

A foundation composition comprising the compounds below is prepared:Phase A Cetyldimethicone copolyol 3 g (Abil EM 90 from the companygoldschmidt) Isostearyl diglyceryl succinate 0.6 g (Imwitor 780K fromthe company Condea) Isododecane 18.5 g Mixture of pigments (hydrophobictitanium 10 g oxides and iron oxides) Polymer of Example 5 8.7 g AMPolyamide powder (Nylon-12 from Dupont) 8 g Fragrance 0.5 g Phase BWater qs 100 Magnesium sulphate 0.7 g Preserving agent (methyl paraben)0.2 g Phase C Water 2 g Preserving agent (diazolinylurea) 0.25 g

Example 22 Nail Varnish

Polymer of Example 12 23.8 g AM Butyl acetate 24.99 g Isopropanol 10.71g Hexylene glycol 2.5 g DC Red 7 Lake 1 g Hectorite modified withstearyldimethylbenzylammonium 1.3 g chloride (Bentone ® 27V fromElementis) Ethyl acetate qs 100 g

Example 23 Mascara Composition

Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g Hectorite modified withdistearyldimethylbenzylammonium 5.3 g chloride (Bentone ® 38V fromElementis) Propylene carbonate 1.7 g Filler 1 g Pigments 5 g Polymer ofExample 14 12 g AM Isododecane qs 100

Example 24 Lipstick in Stick Form

Polyethylene wax 15% Polymer of Example 13 10% AM Hydrogenatedpolyisobutene (Parleam from Nippon 26% Oil Fats) Isododecane qs 100Pigments 8.6% 

Example 25 W/O Foundation

Phase A Cetyldimethicone copolyol 3 g (Abil EM 90 from the companygoldschmidt) Isostearyl diglyceryl succinate 0.6 g (Imwitor 780K fromthe company Condea) Isododecane 18.5 g Mixture of pigments (hydrophobictitanium 10 g oxides and iron oxides) Polymer of Example 15 8.7 g AMPolyamide powder (Nylon-12 from Dupont de 8 g Nemours) Fragrance 0.5 gPhase B Water qs 100 Magnesium sulphate 0.7 g Preserving agent (methylparaben) 0.2 g Phase C Water 2 g Preserving agent (diazolinylurea) 0.25g

Example 26 W/O Foundation

Phase A Mixture of oxypropylated oxyethylated 1.8 g dimethylpolysiloxaneand of cyclodimethylpentasiloxane (85/15) (Abil EM 97 from the companygoldschmidt) Isostearyl diglyceryl succinate 0.6 g (Imwitor 780K fromthe company Condea) Cylcopentadimethylsiloxane 6 g Isododecane qsp 100 gMixture of pigments (hydrophobic titanium 10 g oxides and iron oxides)Polymer of Example 4 2.1 g AM Polyamide powder (Nylon-12 from Dupont) 8g Phase B Water 41.4 g Magnesium sulphate 0.7 g Preserving agent 0.3 g

Example 27 W/O Foundation

Phase A Mixture of oxypropylated oxyethylated 1.8 g dimethylpolysiloxaneand of cyclodimethylpentasiloxane (85/15) (Abil EM 97 from the companyGoldschmidt) Isostearyl diglyceryl succinate 0.6 g (Imwitor 780K fromthe company Condea) Cylcopentadimethylsiloxane 6 g Isododecane qsp 100 gMixture of pigments (hydrophobic titanium 10 g oxides and iron oxides)Polymer of Example 10 2.1 g AM Polyamide powder (Nylon-12 from Dupont) 8g Phase B Water 41.4 g Magnesium sulphate 0.7 g Preserving agent 0.3 g

1-89. (canceled)
 90. A process for preparing a block polymer comprisingat least one first block and at least one second block that areincompatible with each other and that have different glass transitiontemperatures (Tg), wherein the at least one first and second blocks arelinked together via an intermediate segment comprising at least oneconstituent monomer of the at least one first block and at least oneconstituent monomer of the at least one second block, and wherein theblock polymer has a polydispersity index I of greater than 2, theprocess comprising: introducing a portion of polymerization solvent intoa suitable reactor and heating until an adequate temperature forpolymerization is reached, once the polymerization temperature isreached, introducing the constituent monomers of the first block in thepresence of an polymerization initiator, after a time T corresponding toa maximum degree of conversion of 90%, introducing the constituentmonomers of the second block and the rest of the polymerization solvent,leaving the mixture to react for a time T′, then cooling the mixture toroom temperature to obtain the polymer dissolved in the polymerizationsolvent.
 91. The process according to claim 90, wherein thepolymerization temperature ranges from 60 to 120° C.
 92. A cosmeticcomposition comprising at least one block polymer comprising at leastone first block and at least one second block that are incompatible witheach other and that have different glass transition temperatures (Tg),wherein the at least one first and second blocks are linked together viaan intermediate segment comprising at least one constituent monomer ofthe at least one first block and at least one constituent monomer of theat least one second block, and wherein the at least one block polymerhas a polydispersity index I of greater than
 2. 93. The cosmeticcomposition according to claim 92, wherein said composition comprisesfrom 0.1% to 60% by weight of polymer active material.
 94. The cosmeticcomposition according to claim 93, wherein said composition comprisesfrom 5% to 50% by weight of polymer active material.
 95. The cosmeticcomposition according to claim 94, wherein said composition comprisesfrom 10% to 40% by weight of polymer active material.
 96. The cosmeticcomposition according to claim 92, wherein said composition comprises aphysiologically acceptable medium.
 97. The cosmetic compositionaccording to claim 96, wherein said physiologically acceptable mediumcomprises a hydrophilic medium comprising at least one of water andmixtures of water and at least one hydrophilic organic solvent.
 98. Thecosmetic composition according to claim 97, wherein said at least onehydrophilic organic solvent is chosen from alcohols.
 99. The cosmeticcomposition according to claim 98, wherein said alcohols are chosen fromlinear or branched lower monoalcohols comprising from 2 to 5 carbonatoms, polyols, and polyethylene glycols.
 100. The cosmetic compositionaccording to claim 99, wherein said monoalcohols are chosen fromethanol, isopropanol and n-propanol.
 101. The cosmetic compositionaccording to claim 99, wherein said polyols are chosen from glycerol,diglycerol, propylene glycol, sorbitol and pentylene glycol.
 102. Thecosmetic composition according to claim 92, wherein said compositionfurther comprises a fatty phase comprising fatty substances that areliquid or solid at room temperature, and are of animal, plant, mineralor synthetic origin.
 103. The cosmetic composition according to claim92, wherein said composition further comprises at least one cosmeticallyacceptable organic solvent.
 104. The cosmetic composition according toclaim 92, wherein said composition further comprises at least oneauxiliary film-forming agent chosen from plasticizers and coalescers.105. The cosmetic composition according to claim 92, wherein saidcomposition further comprises at least one dyestuff chosen fromwater-soluble dyes and pulverulent dyestuffs.
 106. The cosmeticcomposition according to claim 105, wherein said pulverulent dyestuffsare chosen from pigments, nacres and flakes.
 107. The cosmeticcomposition according to claim 92, wherein said composition furthercomprises at least one filler.
 108. The cosmetic composition accordingto claim 92, wherein said composition further comprises at least oneingredient chosen from vitamins, thickeners, trace elements, softeners,sequestering agents, fragrances, acidifying or basifying agents,preserving agents, sunscreens, surfactants, antioxidants, agents forpreventing hair loss, antidandruff agents and propellants.
 109. Thecosmetic composition according to claim 92, wherein said composition isin the form of a suspension, a dispersion, a solution, a gel, anemulsion, a cream, a mousse, a dispersion of vesicles, a two-phase ormulti-phase lotion, a spray, a powder, or a paste.
 110. The cosmeticcomposition according to claim 109, wherein said emulsion is chosen froman oil-in-water (O/W) emulsion, a water-in-oil (W/O) emulsion and amultiple emulsion (W/O/W or polyol/O/W or O/W/O emulsion).
 111. Thecosmetic composition according to claim 109, wherein said dispersion ofvesicles is chosen from dispersions of ionic and of nonionic lipids.112. The cosmetic composition according to claim 109, wherein said pasteis chosen from a soft paste and an anhydrous paste.
 113. A makeup orcare composition for keratin materials, said composition comprising atleast one block polymer comprising at least one first block and at leastone second block that are incompatible with each other and that havedifferent glass transition temperatures (Tg), wherein the at least onefirst and second blocks are linked together via an intermediate segmentcomprising at least one constituent monomer of the at least one firstblock and at least one constituent monomer of the at least one secondblock, and wherein the at least one block polymer has a polydispersityindex I of greater than
 2. 114. A make-up or care composition accordingto claim 113, wherein said composition is chosen from a haircareproduct, a nail varnish, a lip makeup product, an eye makeup product,and a makeup product for the complexion.
 115. A make-up or carecomposition according to claim 113, wherein the at least one blockpolymer comprises at least one first block having a glass transitiontemperature Tg ranging from 50° C. to 100° C. and at least one secondblock having a glass transition temperature Tg ranging from −100° C. to0° C.
 116. A make-up or care composition according to claim 113, whereinsaid at least one block polymer is chosen from: (i) a block polymercomprising: a first block with a Tg of greater than or equal to 40° C.which is an isobornyl acrylate/isobutyl methacrylate copolymer, a secondblock with a Tg of less than or equal to 20° C. which is a 2-ethylhexylacrylate homopolymer, and an intermediate segment, which is an isobornylacrylate/isobutyl methacrylate/2-ethylhexyl acrylate random copolymer,and (ii) a block polymer comprising: a first block with a Tg of greaterthan or equal to 40° C. which is an isobornyl acrylate/isobutylmethacrylate copolymer, a second block with a Tg of less than or equalto 20° C., which is an isobutyl acrylate homopolymer, and anintermediate segment which is an isobornyl acrylate/isobutylmethacrylate/isobutyl acrylate random copolymer.
 117. A make-up or carecomposition according to claim 116, wherein: in said at least one blockpolymer (i): said first block has a Tg ranging from 0° C. to 20° C.,said second block has a Tg ranging from −85° C. to −55° C., and in saidat least one block polymer (ii): said first block has a Tg ranging from60° C. to 90° C., and said second block has a Tg ranging from −35 to −5°C.
 118. A cosmetic composition according to claim 92, wherein saidcomposition further comprises at least one additional polymer chosenfrom film-forming polymers.
 119. A cosmetic composition according toclaim 92, wherein said composition further comprises at least one fattysubstance which is solid at room temperature and which is chosen fromwaxes, pasty fatty substances and gums.
 120. A cosmetic process formaking up or caring for keratin materials, comprising applying tokeratin materials a cosmetic composition comprising at least one blockpolymer comprising at least one first block and at least one secondblock that are incompatible with each other and that have differentglass transition temperatures (Tg), wherein the at least one first andsecond blocks are linked together via an intermediate segment comprisingat least one constituent monomer of the at least one first block and atleast one constituent monomer of the at least one second block, andwherein the at least one block polymer has a polydispersity index I ofgreater than
 2. 121. A process for improving the staying power of acosmetic composition on keratin materials, comprising applying tokeratin materials a cosmetic composition comprising at least one blockpolymer comprising at least one first block and at least one secondblock that are incompatible with each other and that have differentglass transition temperatures (Tg), wherein the at least one first andsecond blocks are linked together via an intermediate segment comprisingat least one constituent monomer of the at least one first block and atleast one constituent monomer of the at least one second block, andwherein the at least one block polymer has a polydispersity index I ofgreater than 2.